201219344 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種金屬與陶瓷的連接方法及製得的連接件 ，尤其涉及一種不銹鋼與碳化矽陶瓷的連接方法及製得 的連接件。 【先前技術】 [0002] 不銹鋼在常溫下具有較好的耐腐蝕性能，被廣泛應用於 製造各種工程結構和機械零件。然而，當在高溫、腐蝕 性等較為惡劣的環境下使用時，不銹鋼的耐腐蝕性、耐 f) 磨性 '抗沖蝕性、耐高溫性能等e*經很難滿足現代生產 技術的進一步需求。而碳化矽陶瓷具有硬度高、高溫抗 腐蝕、耐磨損、抗沖蝕等優點，因此，不銹鋼和碳化矽 陶瓷連接在一起製備成複合結構，對於不銹鋼在惡劣環 境中應用具有非常重要的意義。 [0003] 目前，實現不銹鋼與碳化矽陶瓷的連接主要是在兩者間 添加中間單層或多層金屬層，在高溫下實現兩者的擴散 Q 連接。採用單層金屬屠難於形成熱膨脹係數的階梯式變 化，在降低熱應力上作用有限，不銹鋼與碳化矽陶瓷的 結合力欠佳。而目前採用的多層金屬層更注重中間金屬 層的活性和相互間的反應，未能充分考慮到熱膨脹係數 要形成階梯式變換，不能大幅降低熱應力。另外，採用 三層以上的中間金屬層還會造成中間金屬層的製備難度 加大’增加成本。 【發明内容】 [0004] 有鑒於此，有必要提供一種易於實現的、可獲得較高連 099138780 表單编號A0I01 第3頁/共13頁 0992067576-0 201219344 接強度的 [0005] [0006] [0007] [0008] [0009] [0010] [0011] [0012] „, 戈化石夕陶瓷的連接方法。 另外，還有必要提供〜 。 、種由上述連接方法製得的連接件 與碳化 夕陶瓷的連接方法，包括以下步驟： 種不銹鋼 提供—不銹鋼件、〜 、〜碳化矽陶瓷件、一鉬箔及一鈦箔； 對該不銹铜件、妒 磨和清洗. 灭化矽陶瓷件、鉬箔及鈦箔分別進行打 將碳化矽陶瓷件 具中 、鉬箔 '欽箔及不銹鋼件放入一連接模 門、 $和鈇箔失放在碳化石户陶瓷件與不銹鋼件之 '翻名與碳化矽陶瓷件相鄰’鈥结與不銹鋼件相 鄰； 將連接核具放人—熱壓燒結爐中，在保護氣氛下對工件 進行固相擴散連接； 待冷卻後取出不銹鋼與碳化瓷的連接件。 一種不銹鋼與碳化矽陶瓷的秦:接件’包括一不銹鋼件、 一碳化矽陶瓷件及連接該不銹鋼件與該碳化矽陶莞件的 連接層’該連接層包括一第一過渡層、一鉬層、一第二 過渡層、一鈦層及一第三過渡層’該第一過渡層位於碳 化矽陶瓷件與鉬層之間，第一過渡層主要由鉬與碳的化 合物、鉬與矽的化合物組成，該第二過渡層位於鉬層與 鈦層之間’第二過渡層主要由鉬鈦固熔體及錮鈦金屬間 化合物組成，該第三過渡層位於鈦層與不銹鋼件之間， 第三過渡層主要由鈦與鐵的固熔體、鐵鈦金屬間化合物 099138780 表單編號A0101 第4頁/共13頁 0992067576-0 201219344 組成。 [0013] Ο 在=技術’上_鋼〜陶究的連接方法 杳、、' 山1。爐中通過施加㈣和㈣作為中間介質層， 實現奴化矽陶瓷件與不銹鋼件的 曰 V1 相擴散連接。在碳化 側施加膨脹係數與碳―相近的㈣作 、接，丨t，銦與碳化石夕陶变較容易發生反應結人 不錄鋼1施加熱雜錄與不_相相鈦=為連 接介質，域的_係數介於不_錢之間，同時欽 與钥能實現良好結合；如此，魏*誠錮、銳不 錄鋼的熱膨脹係數逐漸增大，形成了碳切陶究至不錢 鋼的階梯式變化’有效降低了熱應力，提高了結合力。 且各金屬間產生的金制化合物較少，不會造成結合強 度下降。 … 【實施方式】 [0014] G [0015] 請參閱圖1，本發明較佳實施例的不錄鋼與碳切陶究的 連接方法主要通過固相擴散來完成，該方法主要包括如 下步驟： [0016] 099138780 ⑴提供魏接的碳切喊件2G和不仙賴，同時 提供㈣4G和㈣5G作為連接介f。該mi4〇的厚度大 約為〇·卜Q.2mm’鈦_的厚度大約為0.2〜0.4韻。 ()子碳化石夕陶莞件20、不錄鋼件3〇、翻羯4〇和钦箔 5〇分別進行打磨、清洗，並吹幹。本實施_金剛石砂 打磨反化發陶:£件2〇，用碳化⑦砂紙對不錢鋼件3〇、 muo和鈦㈣進行打磨，使破切陶究件2〇 、不銹鋼 件表3單0編號和鈦表面較為平整，再用盛裝有乙醇 頁/共 13 頁- 0992067576-0 201219344 的超喊進行振動清郎〜15分鐘 2〇、不錄鋼件30、錮落4〇和欽1/去钱石夕陶竟件 清洗後吹幹備用。4〇 —表面雜質及油污等， [0017] [0018] [0019] :蚊化石夕陶变件2〇、銦羯4〇、鈦 3〇依序放人-連接模具獅，使鉬銹鋼件 碳化矽陶瓷件, 、'名5〇夾放在 免件20與不銹鋼件3〇之間， 矽陶瓷件20相鄰，鈦冷40與碳化 具70包括上二广 錢鋼件3°相鄰。該連接模 〇以上壓頭72'下壓頭74 —模腔〔圖去-、 丁悍…口亥中模76具有 下_未不）’用於容置待連接工件。 和下壓頭74分別從兩端將放置於模腔中的工件壓緊該 連接模具70可以為石墨材料製成。 (4)將連接模具70放入—熱壓燒結爐1〇〇中在保護氣 乳下對工件進行固相擴散連接。連接模具7〇放入熱壓燒 結爐100後對熱壓燒結爐100抽真空至^-3“級然後充 入氬氣作為保護氣氛，充入氬氣後熱壓燒結爐1〇〇内壓力 可為0. 3~0. 6MPa。在保護氣氛下將熱壓燒結爐ι〇〇升溫 ’並在如下工藝參數下對主件進行固相擴散連接：升溫 速率為10〜50。〇/ min，連接時溫度為1000〜12〇〇，連 接時溫度的保溫時間為30~60min，軸向壓力為 1〇~40MPa。轴向壓力的具體施加方法為：上壓頭72和下 壓頭74開始對工件施加lOMPa的轴向壓力，加熱，在溫度 到達300°C後慢慢增大軸向壓力，直至溫度為連接時溫度 時，軸向壓力為最大值。 (5)待冷卻後取出不銹鋼件30與碳化石夕陶瓷件2〇的連接 件。 099138780 表單編號A0101 第6頁/共13頁 0992067576-0 201219344 [0020] Ο 上述不銹鋼與碳化矽陶瓷的連接方法在熱壓燒結爐100中 通過施加鉬箔40和鈦箔50作為中間介質層，實現碳化矽 陶瓷件20與不銹鋼件30的固相擴散連接。在碳化矽陶瓷 件一侧施加膨脹係數與碳化矽陶瓷相近的鉬箱作為連接 介質，鉬與碳化矽陶瓷較容易發生反應結合，在不銹鋼 一侧施加熱膨脹係數與不銹鋼相近的鈦箔作為連接介質 ，且鈦的膨脹係數介於不銹鋼與鉬之間，同時鉬與鈦能 實現良好結合；如此，碳化石夕m欽、不錢鋼的 熱膨脹係數逐漸增大，形成了碳化矽陶瓷至不銹鋼熱膨 脹係數的階梯式變，’有效降低了熱應力提高結合力。 且各金屬間產生的金屬間化合物較少，不會造成結合強 度下降。 [0021] Ο 圖2所不為由上述連接方法製得的顿辦碳切陶究的 連接件10，包括該碳切陶究侧、該相鋼件3〇及連 接該不錄鋼件30與該碳化坪喊_的連舞層層8〇。該 連接層8G包括-第-過渡層8卜_銷層“、—第二過渡 廣83、-鈦層咖―第三過渡祕。該第—過渡層⑴立 於碳化㈣:聽2G與翻層H第—過渡層Μ主要由 翻與碳的化合物、！S與石夕的化合物組成，如碳化麵顧 化石夕等。該第二過渡層83位於翻層82與紐層84之間， 其為銷層82與鈦層84連接的過渡層。第二過渡層83主要 由鉬鈦固熔體及鉬鈦金屬間化合物組成。該第三過渡層 85位於鈦細與不_件觀間，其為鈦㈣與不錄鋼 件30連接的過渡層。第三過渡層85主要由欽與鐵的固炫 體、鐵欽金屬間化合物組成。 099138780 表單編號A0101 第7頁/共13頁 0992067576-0 201219344 [0022] 該不銹鋼與碳化矽陶瓷的連接件10的連接層80緻密均勻 ，無裂縫，無孔隙。經測試，該不銹鋼與碳化矽陶瓷的 連接件1 0的不銹鋼/碳化矽陶瓷介面的剪切強度可達 50〜80MPa，抗拉強度達60〜lOOMPa。 【圖式簡單說明】 [0023] 圖1係本發明較佳實施例不銹鋼與碳化矽陶瓷的連接方法 原理圖。 [0024] 圖2係本發明較佳實施例的不銹鋼與碳化矽陶瓷的連接件 的剖面示意圖。 【主要元件符號說明】 [0025] 不銹鋼與碳化矽陶瓷的連接件：10 [0026] 碳化矽陶瓷件：20 [0027] 不銹鋼件：30 [0028] 鉬箔：4 0 [0029] 鈦箔：50 [0030] 連接模具：7〇 [0031] 上壓頭：72 [0032] 下壓頭：74 [0033] 中模：76 [0034] 連接層：80 [0035] 第一過渡層：81 099138780 表單編號A0101 第8頁/共13頁 0992067576-0 201219344 [0036] 鉬層：82 [0037] 第二過渡層 ：83 [0038] 鈦層：84 [0039] 第三過渡層 ：85 [0040] 熱壓燒結爐 :100 Ο201219344 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a method for joining metal and ceramics and a connector formed thereby, and more particularly to a method for joining stainless steel and tantalum carbide ceramics and a connector for the same . [Prior Art] [0002] Stainless steel has good corrosion resistance at room temperature and is widely used in the manufacture of various engineering structures and mechanical parts. However, when used in harsh environments such as high temperature and corrosiveness, the corrosion resistance, f), abrasiveness, erosion resistance, and high temperature resistance of stainless steel are difficult to meet the further needs of modern production technology. . Tantalum carbide ceramics have the advantages of high hardness, high temperature corrosion resistance, wear resistance, erosion resistance, etc. Therefore, stainless steel and tantalum carbide ceramics are joined together to form a composite structure, which is very important for the application of stainless steel in harsh environments. [0003] At present, the connection between stainless steel and tantalum carbide ceramics is mainly achieved by adding an intermediate single layer or a plurality of metal layers between the two, and achieving diffusion Q connection at both temperatures. The use of a single-layer metal toughness to form a stepwise change in the coefficient of thermal expansion has a limited effect on reducing thermal stress, and the bonding strength between stainless steel and tantalum carbide ceramics is poor. However, the multi-layer metal layer currently used pays more attention to the activity and mutual reaction of the intermediate metal layer, and fails to fully consider the thermal expansion coefficient to form a stepwise transformation, which cannot greatly reduce the thermal stress. In addition, the use of three or more intermediate metal layers also makes the preparation of the intermediate metal layer more difficult to increase the cost. SUMMARY OF THE INVENTION [0004] In view of this, it is necessary to provide an easy to implement, obtain a higher connection 099138780 Form No. A0I01 Page 3 / Total 13 Page 0992067576-0 201219344 Connection strength [0005] [0006] [ [0010] [0012] [0012] „, the method of joining Gehua Shixi ceramics. In addition, it is also necessary to provide ~, the connection method and the carbonized ceramics prepared by the above connection method The connection method comprises the following steps: a stainless steel piece, a stainless steel piece, a ~, a tantalum carbide piece, a molybdenum foil and a titanium foil; the stainless copper piece, honing and cleaning. Foil and titanium foil are respectively used to insert carbonized tantalum ceramic parts, molybdenum foil 'chnic foil and stainless steel parts into a joint mold door, $ and 鈇 foil lost in carbonized stone ceramic parts and stainless steel parts' The tantalum carbide ceramic parts are adjacent to the 'knot joints and the stainless steel parts; the connecting fixtures are placed in a hot-pressing sintering furnace, and the workpieces are solid-phase diffusion-bonded under a protective atmosphere; after cooling, the connection between the stainless steel and the carbonized porcelain is taken out. Piece of stainless steel and tantalum carbide The ceramic Qin: the connector 'includes a stainless steel member, a tantalum carbide ceramic member and a connecting layer connecting the stainless steel member and the tantalum carbide member. The connecting layer includes a first transition layer, a molybdenum layer, and a second layer. a transition layer, a titanium layer and a third transition layer Between the tantalum carbide ceramic piece and the molybdenum layer, the first transition layer is mainly composed of a compound of molybdenum and carbon, a compound of molybdenum and niobium, the first The second transition layer is located between the molybdenum layer and the titanium layer. The second transition layer is mainly composed of a molybdenum-titanium solid solution and a niobium-titanium intermetallic compound. The third transition layer is located between the titanium layer and the stainless steel member, and the third transition layer is mainly It consists of solid solution of titanium and iron, iron-titanium intermetallic compound 099138780, form number A0101, page 4 / total 13 pages 0992067576-0 201219344. [0013] Ο In the = technology 'on the steel ~ ceramic connection method 杳, , 'Mountain 1. In the furnace, by applying (4) and (4) as the intermediate medium layer, the 曰V1 phase diffusion connection between the enamel ceramic parts and the stainless steel parts is realized. The expansion coefficient is applied to the carbonization side and the carbon is similar (4). , indium and carbon carbide It is easy to react and the result is not recorded. 1 Applying hot miscellaneous and non-phase phase Ti = for connecting medium, the _ coefficient of the domain is between _ money, and Qin and the key can achieve a good combination; thus, Wei Zheng The coefficient of thermal expansion of 锢 and sharp unrecorded steel is gradually increasing, forming a stepwise change from carbon cut ceramics to no steel. 'The heat stress is effectively reduced, the bonding force is improved, and the amount of gold compounds produced between the metals is less. [0014] Referring to FIG. 1, the connection method of the non-recorded steel and the carbon cut ceramics according to the preferred embodiment of the present invention is mainly completed by solid phase diffusion. The method mainly comprises the following steps: [0016] 099138780 (1) Providing the carbon-cutting 2G of the Wei-connected and not the Xianlai La, while providing (4) 4G and (4) 5G as the connection medium f. The thickness of the mi4 crucible is about 0.2 to 0.4 rhombus. () Sub-carbonized fossil yoke pottery pieces 20, non-recorded steel parts 3 〇, 羯 羯 4 〇 and 箔 箔 〇 〇 〇 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦 钦This implementation _ diamond sand grinding counter-chemical pottery: £ 2 〇, with carbonized 7 sandpaper for the steel parts 3〇, muo and titanium (four) polished, so that the cut-cut ceramics pieces 2 〇, stainless steel parts table 3 single 0 The number and the surface of the titanium are relatively flat, and then vibrate with a super shout of the page containing ethanol / 13 pages - 0992067576-0 201219344 to clear the lang ~ 15 minutes 2 〇, do not record steel parts 30, fallen 4 〇 and Qin 1 / go Qian Shi Xi Tao actually washed and then dried for use. 4〇—surface impurities and oil stains, etc. [0019] [0019]: Mosquito fossil terracotta pieces 2 〇, indium 羯 4 〇, titanium 3 〇 in order to release people - connect the mold lion, make molybdenum rust steel pieces The bismuth carbide ceramic piece, the 'name 5 〇 clip is placed between the free piece 20 and the stainless steel piece 3 ,, the 矽 ceramic piece 20 is adjacent, and the titanium cold 40 and the carbonization tool 70 are adjacent to the 2nd wide carbon steel piece. The connecting die 〇 upper pressing head 72' lower pressing head 74 - the cavity (Fig. -, Ding 悍 口 中 中 中 具有 具有 具有) has been used to accommodate the workpiece to be connected. The lower pressing head 74 presses the workpiece placed in the cavity from both ends, respectively. The connecting die 70 may be made of a graphite material. (4) The joining mold 70 is placed in a hot press sintering furnace 1 to perform solid phase diffusion bonding of the workpiece under protective air. After the mold 7 is placed in the hot press sintering furnace 100, the hot press sintering furnace 100 is evacuated to a level of -3" and then argon gas is charged as a protective atmosphere. After the argon gas is charged, the pressure inside the hot press sintering furnace can be 1 〇〇. 0. 3~0. 6MPa. The hot-pressed sintering furnace is heated under a protective atmosphere and the solid phase diffusion connection is carried out on the main part under the following process parameters: heating rate is 10~50. 〇/min, connection The temperature is 1000~12〇〇, the holding time of the temperature is 30~60min, and the axial pressure is 1〇~40MPa. The specific application method of the axial pressure is: the upper pressing head 72 and the lower pressing head 74 start to the workpiece Apply axial pressure of lOMPa, heat, and slowly increase the axial pressure after the temperature reaches 300 °C, until the temperature is the temperature at the connection, the axial pressure is the maximum value. (5) After cooling, take out the stainless steel piece 30 and Connector for carbon carbide ceramic parts 2〇 099138780 Form No. A0101 Page 6 / Total 13 pages 0992067576-0 201219344 [0020] Ο The above method of joining stainless steel and tantalum carbide ceramics is applied by applying molybdenum foil in hot press sintering furnace 100 40 and titanium foil 50 as an intermediate medium layer to realize carbonized enamel The solid phase diffusion connection of the piece 20 with the stainless steel piece 30. A molybdenum box having a coefficient of expansion similar to that of the tantalum carbide ceramic is applied as a connecting medium on the side of the tantalum carbide ceramic piece, and the molybdenum and the tantalum carbide ceramic are more susceptible to reaction bonding, and are applied on the stainless steel side. Titanium foil with thermal expansion coefficient similar to that of stainless steel is used as the connecting medium, and the expansion coefficient of titanium is between stainless steel and molybdenum. At the same time, molybdenum and titanium can achieve good combination. Thus, the thermal expansion coefficient of carbon carbide shimuqin and yueqian steel increases gradually. Large, forming a stepwise change of the thermal expansion coefficient of tantalum carbide ceramic to stainless steel, 'effectively reduces the thermal stress and improves the bonding force. And the intermetallic compound produced between the metals is less, and the joint strength is not lowered. [0021] 2 joints 10 which are not made by the above connecting method, include the carbon cut ceramic side, the steel part 3该, and the unrecorded steel part 30 and the carbonized flat shouting_ The layer of the dance layer 8G includes a -first-transition layer 8 _ pin layer ", a second transition width 83, a titanium layer coffee - a third transition secret. The first-transition layer (1) is based on carbonization (4): listening to 2G and layering H-transition layer Μ mainly by compounding with carbon,! The composition of the compound of S and Shi Xi, such as the carbonized surface of the fossil. The second transition layer 83 is located between the flip layer 82 and the layer 84, which is a transition layer between the pin layer 82 and the titanium layer 84. The second transition layer 83 is mainly composed of a molybdenum-titanium solid solution and a molybdenum-titanium intermetallic compound. The third transition layer 85 is located between the titanium thin and the non-piece view, which is a transition layer of titanium (four) connected to the unrecorded steel member 30. The third transition layer 85 is mainly composed of a solid spheroid of Ting and iron, and an intermetallic compound of Tieqin. 099138780 Form No. A0101 Page 7 of 13 0992067576-0 201219344 [0022] The connecting layer 80 of the connecting member 10 of the stainless steel and the tantalum carbide ceramic is dense and uniform without cracks and voids. It has been tested that the stainless steel/cerium carbide ceramic interface of the stainless steel and tantalum carbide ceramic joint 10 has a shear strength of 50 to 80 MPa and a tensile strength of 60 to 100 MPa. BRIEF DESCRIPTION OF THE DRAWINGS [0023] Fig. 1 is a schematic view showing a method of joining stainless steel and tantalum carbide ceramics according to a preferred embodiment of the present invention. 2 is a cross-sectional view showing a connecting member of a stainless steel and a tantalum carbide ceramic according to a preferred embodiment of the present invention. [Main component symbol description] [0025] Connector of stainless steel and tantalum carbide ceramic: 10 [0026] Tantalum carbide ceramic member: 20 [0027] Stainless steel member: 30 [0028] Molybdenum foil: 4 0 [0029] Titanium foil: 50 [0030] Connecting mold: 7〇[0031] Upper pressing head: 72 [0032] Lower pressing head: 74 [0033] Medium mold: 76 [0034] Connecting layer: 80 [0035] First transition layer: 81 099138780 Form number A0101 Page 8 of 13 0992067576-0 201219344 [0036] Molybdenum layer: 82 [0037] Second transition layer: 83 [0038] Titanium layer: 84 [0039] Third transition layer: 85 [0040] Hot press sintering Furnace: 100 Ο
099138780 表單編號Α0101 第9頁/共13頁 0992067576-0099138780 Form number Α0101 Page 9 of 13 0992067576-0